US5138113A - Process for producing alkylaromatic hydrocarbons from natural gas - Google Patents

Process for producing alkylaromatic hydrocarbons from natural gas Download PDF

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US5138113A
US5138113A US07/618,423 US61842390A US5138113A US 5138113 A US5138113 A US 5138113A US 61842390 A US61842390 A US 61842390A US 5138113 A US5138113 A US 5138113A
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hydrocarbons
toluene
hydrogen
acetylene
ethylene
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US07/618,423
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Bernard A. Juguin
Jean-Claude P. S. Collin
Joseph Y. M. Larue
Christian R. Busson
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IFP Energies Nouvelles IFPEN
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/02—Monocyclic hydrocarbons
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/40—Ethylene production
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S585/00—Chemistry of hydrocarbon compounds
    • Y10S585/929—Special chemical considerations
    • Y10S585/943—Synthesis from methane or inorganic carbon source, e.g. coal

Definitions

  • the present invention relates to a process for producing alkylaromatic hydrocarbons from natural gas.
  • the process according to the invention comprises three main successive stages :
  • Stage 1) of the thermal cracking of natural gas, more particularly methane, is performed in the presence of hydrogen, at a temperature generally ranging from 900° to 1,400° C., for example at about 1,200° C., preferably in a multichannel reactor made of silicon carbide through whose channels a heat-carrying fluid flows.
  • This reaction which notably generates hydrogen, C 2 + hydrocarbons (particularly ethylene and acetylene), heavy hydrocarbons (C 7 + hydrocarbons (except toluene)), is for example described in French patent applications 2,589,859, 2,596,046 and 2,600,329.
  • Stage 2) of separation of the C 2 + hydrocarbons advantageously comprises the following successive stages :
  • stage 1) a quenching tower where said heavy hydrocarbons are at least partly absorbed in a heavy solvent, of the gas oil or oil type, and withdrawn at the bottom of the quenching tower, and where a gaseous phase is collected at the head of the quenching tower,
  • Phase 3 of conversion of the C 2 30 hydrocarbons into alkylaromatics advantageously comprises the following successive stages :
  • This reaction of selective hydrogenation of acetylene is usually carried out in the presence of at least one catalyst arranged for example in the form of a fixed bed, said catalyst preferably consisting of at least one hydrogenizing metal, most often palladium, deposited on a substantially neutral support; such a catalyst is notably described in French patent application 2,552,078.
  • the reaction temperature (stage i)) generally ranges from about 0° to 100° C., under a pressure ranging from about 0.1 to 10 MPa (the temperature preferably ranges from about 10° to 60° C.
  • the reaction of alkylation of toluene, notably by ethylene (stage iii)), is generally achieved in the presence of at least one acid zeolitic catalyst arranged for example in the form of a fixed bed, usually at a temperature ranging from about 50° to 350° C. (preferably from about 150° to 300° C.), under a pressure ranging from 1 to 10 MPa (preferably from 2 to 7 MPa), with a liquid hydrocarbons flow rate (space velocity) ranging from about 0.2 to 5 volumes per volume of catalyst and per hour and with a molar ratio toluene/ethylene at the inlet of the alkylation reactor ranging from 0.5 to 20 (preferably from 2 to 15).
  • at least one acid zeolitic catalyst arranged for example in the form of a fixed bed, usually at a temperature ranging from about 50° to 350° C. (preferably from about 150° to 300° C.), under a pressure ranging from 1 to 10 MPa (preferably from 2 to 7 MPa), with a liquid hydrocarbons flow rate
  • the catalyst used in stage iii) is preferably based on a dealuminized mordenite with a total atomic ratio Si/Al ranging from 20 to 60; this catalyst is notably described in French patent applications 87/12,932, 88/14,099 and 88/17,164.
  • Natural gas essentially comprising methane is subjected to a thermal cracking reaction at high temperature in a multichannel reactor made of silicon carbide; at the outlet of said reactor, the effluent consists of hydrogen, methane, acetylene, ethylene, ethane, propene, butanes, benzene, toluene and C 7 hydrocarbons.
  • the effluent from the outlet of the thermal cracking reactor is cooled down to 200°-350° C. and injected into a quenching tower in which the heaviest hydrocarbons as well as the soots are absorbed in a heavy solvent of the gas oil or oil type.
  • the liquid phase formed is pumped at the bottom of the quenching tower, cooled and recycled to the head; a pure solvent addition and a withdrawal are generally performed in order to avoid an accumulation of absorbed product.
  • the gaseous phase from the quenching tower is compressed between 3 and 5 MPa, for example at 4 MPa. Considering the rate of compression, the latter is preferably carried out in several stages with intermediate cooling. At the compressor outlet, the flow is brought back to a temperature close to the room temperature (15° to 25° C.), in order to condense the traces of heavy compounds (notably benzene and C 7 hydrocarbons), which are usually recycled towards the quenching tower.
  • 3 and 5 MPa for example at 4 MPa.
  • the latter is preferably carried out in several stages with intermediate cooling.
  • the flow is brought back to a temperature close to the room temperature (15° to 25° C.), in order to condense the traces of heavy compounds (notably benzene and C 7 hydrocarbons), which are usually recycled towards the quenching tower.
  • the excess hydrogen generated by the cracking of the methane is separated by gaseous permeation. To that end, the flow is preheated in order to deviate from the dew point and then introduced into a permeator.
  • the extracted hydrogen has a low pressure and is practically pure. This hydrogen flow can possibly be recycled in the further stage of selective hydrogenation of acetylene.
  • the fraction of C 2 + hydrocarbons is then separated from the hydrogen and the non converted methane (which are recycled to the thermal cracking reactor) by absorption. This operation is for example achieved by counterflow contact with cold toluene.
  • the necessity of a high C 2 + recovery rate (generally higher than 97%) most often imposes operating conditions with a high pressure (for example about 4 MPa), a low temperature (for example about -40° C.) and a solvent rate usually higher than 1.
  • the liquid phase from the cooled absorption stage which also contains a proportion of methane co-absorbed in the solvent, is sent in its entirety to the sagate of selective hydrogenation of acetylene.
  • the aqueous phase coming out at the head of the cooled absorption unit is expanded in a turbine.
  • the cold produced thereby allows to ensure the total cooling that is necessary for the absorption.
  • the mechanical work of expansion is recovered at the level of the compressors.
  • the expanded flow is generally recycled to the thermal cracking reactor.
  • the liquid phase from the cooled absorption stage is then subjected to a selective hydrogenation the aim of which is to selectively convert the acetylene into ethylene.
  • the operation is generally carried out with excess hydrogen (for example from 10 to 35%) in relation to the stoichiometry.
  • the hydrogen can either come from the permeator (which causes an additional compression), or from the mixture of hydrogen and methane from the cooled absorption stage.
  • the amount of toluene contained in the flow from the selective hydrogenation stage is generally an excess amount for the alkylation stage.
  • the molar ratio toluene/ethylene is generally higher than 20, whereas a value ranging from 7 to 15 is preferably required for the alkylation reaction.
  • a separation by distillation of the toluene and the alkyltoluenes planned after the alkylation would be costly, since the main constituent, that is to say toluene, should be withdrawn at the column head. It is therefore necessary to separate before the alkylation the toluene that is not essential for this stage.
  • the toluene is at least partly removed the mixture is expanded at low pressure and fractionated in a column; the toluene withdrawn at the bottom is generally recycled to the cooled absorption stage, the topping gas being repressured and sent to the alkylation stage.
  • this topping gas containing the ethylene is mixed with excess toluene (generally 7 to 15 times the stoichiometry).
  • the obtained mixture is heated up between about 240° and 300° C., and then sent into an alkylation reactor where the ethylene and at least part of the toluene are converted notably into ethyltoluene and polyethyltoluenes.
  • the effluent comprising the alkyltoluenes and the excess toluene is expanded and the effluent is injected into a second distillation column.
  • the flow coming out at the column head essentially consists of hydrogen, methane, ethane, butanes and toluene. This flow is cooled down, and then sent into a condenser.
  • the residual gaseous fraction (essentially methane and hydrogen) coming out at the condenser head is generally recycled to the thermal cracking reactor.
  • the liquid fraction withdrawn at the condenser bottom (essentially toluene) is partly injected as a reflux into the second distillation column and partly recycled upstream from the alkylation reactor with generally make-up toluene to compensate for the part converted into alkyltoluenes.
  • the alkyltoluenes are collected at the bottom of the second distillation column and sent for example to the gasoline pool of a refinery.
  • the attached Figure is a schematic flowsheet of a comprehensive embodiment of the invention.
  • a feedstock (2) consisting of a mixture of fresh natural gas (1), essentially comprising methane, of gas (3) from the head of absorber (24) and of gas (4) from the head of the condenser (47) is introduced into a thermal cracking section (5).
  • Said feedstock (2) shows the following composition (expressed in kilogram) :
  • the feedstock is thus preheated at about 600° C. and then cracked in a multichannel pyrolysis zone made of silicon carbide.
  • a heat-carrying fluid consisting of burner combustion fumes at about 1,400° C. is sent across the channels meant for this use at a flow rate such that the temperature of the effluent mixture at the pyrolysis outlet is about 1,200° C.; the residence time of the feedstock in this zone is about 300 milliseconds.
  • the temperature of the gaseous effluent is about 250° C.
  • This gaseous effluent coming out of (5) has, after cooling down (6) to the room temperature, the following composition (expressed in kilogram) :
  • 1,056 kg of heavy products which are cooled (12) and recycled (13) at the top of the quenching tower, after a possible addition of heavy solvent (10), are withdrawn.
  • These 1,056 kg of heavy products have the following composition:
  • a withdrawal (14) can possibly be carried out notably in order to avoid an accumulation of absorbed products.
  • This gaseous phase is then compressed at 4 MPa (16) and brought back to the room temperature (17); 130 kg of heavy products are thus condensed, separated (18) and recycled (9) towards the quenching tower (7).
  • 130 kg of heavy products have the following composition:
  • 5,649 kg of gas are preheated (19) in order to deviate from the dew point, and introduced into a permeator (20) in order to decrease the excess hydrogen generated by the thermal cracking of the methane.
  • These 5,649 kg of gas have the following composition:
  • the fraction of C 2 + hydrocarbons is substantially separated from the hydrogen and the methane by counterflow contact with 68,120 kg of toluene (25) cooled (26) down to about -40° C. and coming from the bottom (37) of the distillation column (36).
  • This liquid phase is then reheated (31) and sent towards the selective hydrogenation section (32), where, in the presence of a palladium-based catalyst, the acetylene is hydrogenated in the following operating conditions:
  • This effluent is then expanded (35) and sent into a first distillation column (36) to separate the toluene from the lighter hydrocarbons.
  • This gaseous phase is repressured (39) and mixed with 25,538 kg of toluene (40); the resulting mixture, after preheating (41), is sent into an alkylation reactor (42) where the olefin are converted into alkylaromatic hydrocarbons, in the presence of a dealuminized mordenite with a total atomic ratio Si/Al of about 35, in the following operating conditions:
  • This gas is then recycled towards the thermal cracking section (5).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention relates to a process for producing alkylaromatic hydrocarbons from natural gas containing methane, characterized in that it comprises the following three successive stages:
1) thermal cracking of the natural gas with forming of hydrogen and C2 30 hydrocarbons, particularly ethylene and acetylene,
2) separation of the C2 + hydrocarbons, particularly of the ethylene and the acteylene, obtained at the end of stage 1), by cooled absorption in a solvent,
3) conversion of the C2 + hydrocarbons from stage 2) into alkylaromatics.
The obtained alkylaromatics can be used as a base for premium gasoline.

Description

SUMMARY OF THE INVENTION
The present invention relates to a process for producing alkylaromatic hydrocarbons from natural gas.
Until now, the main processes for producing alkylaromatic hydrocarbons were reforming, steam cracking and alkylation. More recently, a new process for aromatizing light paraffins has been mentioned.
The process according to the invention comprises three main successive stages :
1) thermal cracking of the natural gas containing methane (for example 60 to 99% by volume) with forming of hydrogen and C2 + hydrocarbons,
2) separation of the C2 + hydrocarbons, obtained at the end of stage 1), by cooled absorption in a solvent such as toluene,
3) conversion of the C2 + hydrocarbons from stage 2) into alkylaromatics.
Stage 1) of the thermal cracking of natural gas, more particularly methane, is performed in the presence of hydrogen, at a temperature generally ranging from 900° to 1,400° C., for example at about 1,200° C., preferably in a multichannel reactor made of silicon carbide through whose channels a heat-carrying fluid flows. This reaction, which notably generates hydrogen, C2 + hydrocarbons (particularly ethylene and acetylene), heavy hydrocarbons (C7 + hydrocarbons (except toluene)), is for example described in French patent applications 2,589,859, 2,596,046 and 2,600,329.
Stage 2) of separation of the C2 + hydrocarbons advantageously comprises the following successive stages :
a) sending of the effluent from stage 1) into a quenching tower where said heavy hydrocarbons are at least partly absorbed in a heavy solvent, of the gas oil or oil type, and withdrawn at the bottom of the quenching tower, and where a gaseous phase is collected at the head of the quenching tower,
b) compression of the gaseous phase from stage a) in order to remove at least for the most part the remaining heavy products (C7 + hydrocarbons (except toluene) and heavy solvent) from said gaseous phase, usually between 1 and 7 MPa, preferably between 3 and 5 MPa, for example at about 4 MPa,
c) separation of the excess hydrogen, generated by stage 1) and contained in the gaseous phase from stage b), by gaseous permeation,
d) cooled absorption of the C2 + hydrocarbons contained in the gaseous phase from stage c), in a solvent such as toluene in order to substantially separate, on one hand, said C2 + hydrocarbons (particularly ethylene and acetylene), in a liquid phase, and, on the other hand, the hydrogen and the methane, in a gaseous phase.
Phase 3) of conversion of the C2 30 hydrocarbons into alkylaromatics advantageously comprises the following successive stages :
i) selective hydrogenation of the liquid phase comprising the C2 + hydrocarbons (particularly ethylene and acetylene) in order to selectively convert the acetylene into ethylene,
ii) at least partial removal of the toluene contained in the effluent from stage i), said toluene being generally recycled towards stage d),
iii) alkylation of the toluene (which can be different from that which has been removed in stage ii)), by C2 + hydrocarbons (particularly ethylene) contained in the mixture from stage ii).
Acetylene being a poison for catalysts used for the alkylation of toluene by ethylene, it is essential to convert it beforehand by selective hydrogenation (stage i)). This reaction of selective hydrogenation of acetylene is usually carried out in the presence of at least one catalyst arranged for example in the form of a fixed bed, said catalyst preferably consisting of at least one hydrogenizing metal, most often palladium, deposited on a substantially neutral support; such a catalyst is notably described in French patent application 2,552,078. The reaction temperature (stage i)) generally ranges from about 0° to 100° C., under a pressure ranging from about 0.1 to 10 MPa (the temperature preferably ranges from about 10° to 60° C. and the pressure, from about 1 to 6 MPa), with a liquid hydrocarbons flow rate (space velocity) ranging from about 2 to 20 volumes per volume of catalyst and per hour and with a molar ratio hydrogen/acetylene at the inlet of the hydrogenation reactor ranging from 0.5 to 5.
The reaction of alkylation of toluene, notably by ethylene (stage iii)), is generally achieved in the presence of at least one acid zeolitic catalyst arranged for example in the form of a fixed bed, usually at a temperature ranging from about 50° to 350° C. (preferably from about 150° to 300° C.), under a pressure ranging from 1 to 10 MPa (preferably from 2 to 7 MPa), with a liquid hydrocarbons flow rate (space velocity) ranging from about 0.2 to 5 volumes per volume of catalyst and per hour and with a molar ratio toluene/ethylene at the inlet of the alkylation reactor ranging from 0.5 to 20 (preferably from 2 to 15). The catalyst used in stage iii) is preferably based on a dealuminized mordenite with a total atomic ratio Si/Al ranging from 20 to 60; this catalyst is notably described in French patent applications 87/12,932, 88/14,099 and 88/17,164.
DETAILED DESCRIPTION OF THE INVENTION
A particular embodiment of the invention is described hereafter :
Natural gas essentially comprising methane is subjected to a thermal cracking reaction at high temperature in a multichannel reactor made of silicon carbide; at the outlet of said reactor, the effluent consists of hydrogen, methane, acetylene, ethylene, ethane, propene, butanes, benzene, toluene and C7 hydrocarbons.
The effluent from the outlet of the thermal cracking reactor is cooled down to 200°-350° C. and injected into a quenching tower in which the heaviest hydrocarbons as well as the soots are absorbed in a heavy solvent of the gas oil or oil type. The liquid phase formed is pumped at the bottom of the quenching tower, cooled and recycled to the head; a pure solvent addition and a withdrawal are generally performed in order to avoid an accumulation of absorbed product.
The gaseous phase from the quenching tower is compressed between 3 and 5 MPa, for example at 4 MPa. Considering the rate of compression, the latter is preferably carried out in several stages with intermediate cooling. At the compressor outlet, the flow is brought back to a temperature close to the room temperature (15° to 25° C.), in order to condense the traces of heavy compounds (notably benzene and C7 hydrocarbons), which are usually recycled towards the quenching tower.
The excess hydrogen generated by the cracking of the methane is separated by gaseous permeation. To that end, the flow is preheated in order to deviate from the dew point and then introduced into a permeator. The extracted hydrogen has a low pressure and is practically pure. This hydrogen flow can possibly be recycled in the further stage of selective hydrogenation of acetylene.
The fraction of C2 + hydrocarbons is then separated from the hydrogen and the non converted methane (which are recycled to the thermal cracking reactor) by absorption. This operation is for example achieved by counterflow contact with cold toluene. The necessity of a high C2 + recovery rate (generally higher than 97%) most often imposes operating conditions with a high pressure (for example about 4 MPa), a low temperature (for example about -40° C.) and a solvent rate usually higher than 1. The liquid phase from the cooled absorption stage, which also contains a proportion of methane co-absorbed in the solvent, is sent in its entirety to the sagate of selective hydrogenation of acetylene.
The aqueous phase coming out at the head of the cooled absorption unit is expanded in a turbine. The cold produced thereby allows to ensure the total cooling that is necessary for the absorption. The mechanical work of expansion is recovered at the level of the compressors. The expanded flow is generally recycled to the thermal cracking reactor.
The liquid phase from the cooled absorption stage is then subjected to a selective hydrogenation the aim of which is to selectively convert the acetylene into ethylene. The operation is generally carried out with excess hydrogen (for example from 10 to 35%) in relation to the stoichiometry. The hydrogen can either come from the permeator (which causes an additional compression), or from the mixture of hydrogen and methane from the cooled absorption stage.
The amount of toluene contained in the flow from the selective hydrogenation stage is generally an excess amount for the alkylation stage. As a matter of fact, the molar ratio toluene/ethylene is generally higher than 20, whereas a value ranging from 7 to 15 is preferably required for the alkylation reaction. Besides, a separation by distillation of the toluene and the alkyltoluenes planned after the alkylation would be costly, since the main constituent, that is to say toluene, should be withdrawn at the column head. It is therefore necessary to separate before the alkylation the toluene that is not essential for this stage. For this reason, at the end of the selective hydrogenation stage, the toluene is at least partly removed the mixture is expanded at low pressure and fractionated in a column; the toluene withdrawn at the bottom is generally recycled to the cooled absorption stage, the topping gas being repressured and sent to the alkylation stage.
At the compressor outlet, this topping gas containing the ethylene is mixed with excess toluene (generally 7 to 15 times the stoichiometry). The obtained mixture is heated up between about 240° and 300° C., and then sent into an alkylation reactor where the ethylene and at least part of the toluene are converted notably into ethyltoluene and polyethyltoluenes.
At the outlet of the alkylation reactor, the effluent comprising the alkyltoluenes and the excess toluene is expanded and the effluent is injected into a second distillation column. The flow coming out at the column head essentially consists of hydrogen, methane, ethane, butanes and toluene. This flow is cooled down, and then sent into a condenser. The residual gaseous fraction (essentially methane and hydrogen) coming out at the condenser head is generally recycled to the thermal cracking reactor. The liquid fraction withdrawn at the condenser bottom (essentially toluene) is partly injected as a reflux into the second distillation column and partly recycled upstream from the alkylation reactor with generally make-up toluene to compensate for the part converted into alkyltoluenes. The alkyltoluenes are collected at the bottom of the second distillation column and sent for example to the gasoline pool of a refinery.
BRIEF DESCRIPTION OF THE DRAWING
The attached Figure is a schematic flowsheet of a comprehensive embodiment of the invention.
The following example illustrates the invention without limiting the scope thereof.
EXAMPLE AND DETAILED DESCRIPTION OF THE DRAWING
It is illustrated by the sole figure.
A feedstock (2) consisting of a mixture of fresh natural gas (1), essentially comprising methane, of gas (3) from the head of absorber (24) and of gas (4) from the head of the condenser (47) is introduced into a thermal cracking section (5).
Said feedstock (2) shows the following composition (expressed in kilogram) :
______________________________________                                    
       hydrogen                                                           
              661                                                         
       methane                                                            
              4,988                                                       
       ethylene                                                           
               3                                                          
       ethane 35                                                          
       n-butane                                                           
              34                                                          
       toluene                                                            
               2                                                          
              5,723                                                       
______________________________________
The feedstock is thus preheated at about 600° C. and then cracked in a multichannel pyrolysis zone made of silicon carbide. A heat-carrying fluid consisting of burner combustion fumes at about 1,400° C. is sent across the channels meant for this use at a flow rate such that the temperature of the effluent mixture at the pyrolysis outlet is about 1,200° C.; the residence time of the feedstock in this zone is about 300 milliseconds. After passing across a quenching zone (supplied with air as a coolant), the temperature of the gaseous effluent is about 250° C.
This gaseous effluent coming out of (5) has, after cooling down (6) to the room temperature, the following composition (expressed in kilogram) :
______________________________________                                    
hydrogen         948                                                      
methane          3,680                                                    
acetylene        424                                                      
ethylene         339                                                      
ethane            16                                                      
propene           9                                                       
n-butane          34                                                      
benzene          190                                                      
toluene           6                                                       
C.sub.7 hydrocarbons                                                      
                  77                                                      
                 5,723                                                    
______________________________________
This corresponds to a conversion rate per pass of methane of about 26.2%.
These 5,723 kg of gaseous effluent are then sent into a quenching tower (7), at the same time as 1,112 kg of a heavy solvent comprising recycled solvent (9) and fresh make-up solvent (10). The composition of these 1,112 kg is the following :
______________________________________                                    
hydrogen         0.02                                                     
methane          1.12                                                     
acetylene        0.52                                                     
ethylene         0.28                                                     
n-butane         0.58                                                     
benzene          30.42                                                    
toluene          2.76                                                     
C.sub.7 hydrocarbons                                                      
                 32.86                                                    
gas oil          1043.80                                                  
                 1,112                                                    
______________________________________
At the bottom of the quenching tower, 1,056 kg of heavy products which are cooled (12) and recycled (13) at the top of the quenching tower, after a possible addition of heavy solvent (10), are withdrawn. These 1,056 kg of heavy products have the following composition:
______________________________________                                    
methane          0.16                                                     
benzene          4.68                                                     
toluene          0.92                                                     
C.sub.7 hydrocarbons                                                      
                 67.84                                                    
gas oil          982.40                                                   
                 1,056                                                    
______________________________________
A withdrawal (14) can possibly be carried out notably in order to avoid an accumulation of absorbed products.
At the head (15) of this quenching tower, 5,779 kg of gaseous phase with the following composition are collected:
______________________________________                                    
hydrogen         948.02                                                   
methane          3680.96                                                  
acetylene        424.52                                                   
ethylene         339.28                                                   
ethane           16                                                       
propene          9                                                        
n-butane         34.58                                                    
benzene          215.74                                                   
toluene          7.84                                                     
C.sub.7 hydrocarbons                                                      
                 42.02                                                    
heavy solvent    61.04                                                    
                 5,779                                                    
______________________________________
This gaseous phase is then compressed at 4 MPa (16) and brought back to the room temperature (17); 130 kg of heavy products are thus condensed, separated (18) and recycled (9) towards the quenching tower (7). These 130 kg of heavy products have the following composition:
______________________________________                                    
hydrogen         0.02                                                     
methane          0.96                                                     
acetylene        0.52                                                     
ethylene         0.28                                                     
n-butane         0.58                                                     
benzene          30.42                                                    
toluene          2.76                                                     
C.sub.7 hydrocarbons                                                      
                 33.42                                                    
heavy solvent    61.04                                                    
                 130                                                      
______________________________________
After the separation of these heavy products recycled to the quench, 5,649 kg of gas are preheated (19) in order to deviate from the dew point, and introduced into a permeator (20) in order to decrease the excess hydrogen generated by the thermal cracking of the methane. These 5,649 kg of gas have the following composition:
______________________________________                                    
hydrogen         948                                                      
methane          3,680                                                    
acetylene        424                                                      
ethylene         339                                                      
ethane           16                                                       
propene          9                                                        
n-butane         34                                                       
benzene          185.32                                                   
toluene          5.08                                                     
C.sub.7 hydrocarbons                                                      
                 8.60                                                     
                 5,649                                                    
______________________________________
At the permeator outlet, on one hand, 288 kg of pure hydrogen (21) are collected, which can be utilized in another section of the refinery (for example partly in the further stage of selective hydrogenation of acetylene) and, on the other hand, 5,361 kg of gaseous effluent (22) are collected which, after cooling (23), are sent towards an absorber (24). This effluent has the following composition (expressed in kilogram) :
______________________________________                                    
hydrogen         660                                                      
methane          3,680                                                    
acetylene        424                                                      
ethylene         339                                                      
ethane           16                                                       
propene          9                                                        
n-butane         34                                                       
benzene          185.32                                                   
toluene          5.08                                                     
C.sub.7 hydrocarbons                                                      
                 8.60                                                     
                 5,361                                                    
______________________________________
In the absorber (24), the fraction of C2 + hydrocarbons is substantially separated from the hydrogen and the methane by counterflow contact with 68,120 kg of toluene (25) cooled (26) down to about -40° C. and coming from the bottom (37) of the distillation column (36).
After the reaction, 3,158 kg of gas are collected at the head (27) of the absorber and expanded (28), reheated (29) and then recycled (3) towards the thermal cracking section (5). These 3,158 kg of gas have the following composition :
______________________________________                                    
       hydrogen                                                           
              655                                                         
       methane                                                            
              2,498                                                       
       ethylene                                                           
              3                                                           
       toluene                                                            
              2                                                           
              3,158                                                       
______________________________________
At the bottom (30) of the absorber, 70,323 kg of liquid phase with the following composition are withdrawn:
______________________________________                                    
hydrogen        5                                                         
methane         1,182                                                     
acetylene       424                                                       
ethylene        336                                                       
ethane          16                                                        
propene         9                                                         
n-butane        34                                                        
benzene         185.4                                                     
toluene         68,123                                                    
C.sub.7 hydrocarbons                                                      
                8.6                                                       
                70,323                                                    
______________________________________
This liquid phase is then reheated (31) and sent towards the selective hydrogenation section (32), where, in the presence of a palladium-based catalyst, the acetylene is hydrogenated in the following operating conditions:
______________________________________                                    
temperature                20° C.                                  
pressure                    4 MPa                                         
liquid hourly flow rate = 10 times the volume                             
of the catalyst                                                           
molar ratio hydrogen/acetylene = 1.2, that is                             
to say that 34 kg of hydrogen are added (33).                             
______________________________________
At the outlet (34) of the selective hydrogenation section, 70,357 kg of an effluent with the following composition are collected:
______________________________________                                    
hydrogen        6                                                         
methane         1,182                                                     
acetylene       17                                                        
ethylene        757                                                       
ethane          35                                                        
propene         9                                                         
n-butane        34                                                        
benzene         185.4                                                     
toluene         68,123                                                    
C.sub.7 hydrocarbons                                                      
                8.6                                                       
                70,357                                                    
______________________________________
This effluent is then expanded (35) and sent into a first distillation column (36) to separate the toluene from the lighter hydrocarbons.
At the bottom (36) of this distillation column, 68,120 kg of toluene, that ar recycled to the absorber head (24), are withdrawn.
At the head (38) of this distillation column, 2,237 kg of gaseous phase with the following composition are collected:
______________________________________                                    
hydrogen         6                                                        
methane          1,182                                                    
acetylene        17                                                       
ethylene         757                                                      
ethane           35                                                       
propene          9                                                        
n-butane         34                                                       
benzene          185.4                                                    
toluene          3                                                        
C.sub.7 hydrocarbons                                                      
                 8.6                                                      
                 2,237                                                    
______________________________________
This gaseous phase is repressured (39) and mixed with 25,538 kg of toluene (40); the resulting mixture, after preheating (41), is sent into an alkylation reactor (42) where the olefin are converted into alkylaromatic hydrocarbons, in the presence of a dealuminized mordenite with a total atomic ratio Si/Al of about 35, in the following operating conditions:
______________________________________                                    
temperature                270° C.                                 
pressure                    4 MPa                                         
liquid hourly flow rate = twice the volume of                             
the catalyst.                                                             
______________________________________
At the outlet of the alkylation rector, 27,775 kg of a product with the following composition are collected:
______________________________________                                    
hydrogen            6                                                     
methane            1,182                                                  
ethane             35                                                     
n-butane           34                                                     
benzene            167                                                    
toluene            22,917                                                 
C.sub.7 hydrocarbons                                                      
                    9                                                     
ethylbenzene       25                                                     
methylethylbenzenes                                                       
                   3,031                                                  
methyldiethylbenzenes                                                     
                   329                                                    
methylisopropylbenzenes                                                   
                   40                                                     
                   27,775                                                 
______________________________________
After expanding (43), this product is sent into a second distillation column (44).
The product coming out at the head of this distillation column is cooled (46) and then sent into a condenser (47).
At the head (4) of this condenser, 1,257 kg of gas with the following composition are collected:
______________________________________                                    
       hydrogen                                                           
                 6                                                        
       methane                                                            
              1,182                                                       
       ethane   35                                                        
       n-butane                                                           
                34                                                        
              1,257                                                       
______________________________________
This gas is then recycled towards the thermal cracking section (5).
At the bottom (48) of this condenser, 23,084 kg of liquid phase are collected and partly recycled towards the head (49) of the second distillation column (44) to serve as a reflux and partly recycled upstream (40) from the alkylation reactor, after adding make-up toluene (50).
At the bottom (51) of the second distillation column (44), 3,434 kg of product with the following composition are collected :
______________________________________                                    
C.sub.7 hydrocarbons                                                      
                   9                                                      
ethylbenzene      25                                                      
methylethylbenzenes                                                       
                  3,031                                                   
methyldiethylbenzenes                                                     
                  329                                                     
methylisopropylbenzenes                                                   
                  40                                                      
                  3,434                                                   
______________________________________
These 3,434 kg are a good base for premium gasoline and can thus be sent to the gasoline pool of the refinery.
______________________________________                                    
ASTM distillation                                                         
initial point           99° C.                                     
final point            212° C.                                     
octane numbers                                                            
clear RON              110                                                
clear MON              101                                                
______________________________________

Claims (11)

We claim:
1. A process for producing alkylaromatic hydrocarbons from natural gas containing methane, comprising the following successive steps:
1) thermal cracking of the natural gas to form an effluent of hydrogen, C2 + hydrocarbons comprising ethylene and acetylene, and C7 + heavy hydrocarbons,
2) separation of said C2 + hydrocarbons from methane and hydrogen, by cooled absorption in toluene,
3) selectively hydrogenating the resultant toluene phase containing C2 + hydrocarbons to convert acetylene into ethylene; and
3) reacting resultant ethylene-enriched C2 + hydrocarbons from step 3) with toluene, in contact with a catalyst, to from an alkylated toluene.
2. A process according to claim 1, wherein step 1) is carried out in the presence of hydrogen, at a temperature ranging from 900° to 1,400° C., in a multichannel reactor made of silicon carbide, through which channels a heat-carrying fluid flows.
3. A process according to claim 1, wherein step 2) comprises the following successive substeps:
a) sending of the effluent from step 1) into a quenching tower where the heavy hydrocarbons are at least partly absorbed in a heavy solvent and withdrawn at the bottom of said quenching tower, and wherein a gaseous phase containing ethylene and acetylene is collected at the head of said quenching tower,
b) compression between 1 and 7 MPa of the gaseous phase from substep a), in order to at least partially remove remaining heavy products from said gaseous phase,
c) separation of excess hydrogen, generated by step 1) and contained in the gaseous phase from substep b), by gaseous permeation, and
d) cooled absorption of the C2 + hydrocarbons, comprising ethylene and acetylene, contained in the gaseous phase from step c), in toluene, in order to substantially separate said C2 + hydrocarbons comprising ethylene and acetylene, from the hydrogen and the methane.
4. A process according to claim 3, wherein the hydrogen and the methane separated in step d) are recycled to step 1).
5. A process according to claim 1, wherein steps 3 and 4 comprise the following successive substeps:
i) at least partial removal of the toluene contained in the effluent from step 3) and employing the resultant removed toluene in step 4).
6. A process according to claim 3, wherein the excess hydrogen separated by gaseous permeation in substep c) is recycled to substep i).
7. A process according to claim 5, wherein step i) is performed in the presence of at least one catalyst formed by at least one hydrogenizing metal.
8. A process according to claim 1, wherein step 4) is performed in the presence of at least one catalyst based on a dealuminized mordenite with a total atomic ratio Si/Al ranging from 20 to 60.
9. A process according to claim 1, wherein the toluene employed in step (2) is alkylated in step (4).
10. A process for producing alkylaromatic hydrocarbons from natural gas containing methane, comprising the following successive steps:
1) thermal cracking of the natural gas to form hydrogen and C2 + hydrocarbons comprising ethylene and acetylene;
2) subjecting said hydrogen and C2 + hydrocarbons from step (1) to cold absorption in toluene to separate said C2 + hydrocarbons from methane and hydrogen;
3) vaporizing a portion of said toluene from resulting effluent from step (2) and reacting resultant vaporized toluene with at least a portion of the C2 + hydrocarbons to form alkylated toluene.
11. A process according to claim 10, wherein prior to reacting said C2 + hydrocarbons with toluene, removing acetylene from said C2 + hydrocarbons, thereby resulting in an acetylene-depleted C2 + hydrocarbon fractions for the production of alkylated toluenes.
US07/618,423 1989-11-28 1990-11-27 Process for producing alkylaromatic hydrocarbons from natural gas Expired - Fee Related US5138113A (en)

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FR8915767A FR2655038B1 (en) 1989-11-28 1989-11-28 PROCESS FOR PRODUCING ALKYLAROMATIC HYDROCARBONS FROM NATURAL GAS. INVENTION OF MM. BERNARD JUGUIN, JEAN-CLAUDE COLLIN, JOSEPH LARUE AND CHRISTIAN BUSSON.

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US5856607A (en) * 1996-05-03 1999-01-05 Amoco Corporation Process for production of ethylbenzene frome dilute ethylene streams
US6130260A (en) * 1998-11-25 2000-10-10 The Texas A&M University Systems Method for converting natural gas to liquid hydrocarbons
US6602920B2 (en) 1998-11-25 2003-08-05 The Texas A&M University System Method for converting natural gas to liquid hydrocarbons
US6783659B2 (en) * 2001-11-16 2004-08-31 Chevron Phillips Chemical Company, L.P. Process to produce a dilute ethylene stream and a dilute propylene stream
US20070191664A1 (en) * 2005-12-23 2007-08-16 Frank Hershkowitz Methane conversion to higher hydrocarbons
US20080300438A1 (en) * 2007-06-04 2008-12-04 Keusenkothen Paul F Conversion of co-fed methane and hydrocarbon feedstocks into higher value hydrocarbons
US20100130803A1 (en) * 2008-11-25 2010-05-27 Keusenkothen Paul F Conversion of Co-Fed Methane and Low Hydrogen Content Hydrocarbon Feedstocks to Acetylene
US20100126907A1 (en) * 2008-11-24 2010-05-27 Chun Changmin Heat Stable Formed Ceramic, Apparatus And Method Of Using The Same
US20100292523A1 (en) * 2009-05-18 2010-11-18 Frank Hershkowitz Pyrolysis Reactor Materials and Methods
US20100292522A1 (en) * 2009-05-18 2010-11-18 Chun Changmin Stabilized Ceramic Composition, Apparatus and Methods of Using the Same
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US8512663B2 (en) 2009-05-18 2013-08-20 Exxonmobile Chemical Patents Inc. Pyrolysis reactor materials and methods
US8545580B2 (en) 2006-07-18 2013-10-01 Honeywell International Inc. Chemically-modified mixed fuels, methods of production and uses thereof
US20140058154A1 (en) * 2012-08-21 2014-02-27 Uop Llc Nitrogen removal and methane conversion process using a supersonic flow reactor
US20140058152A1 (en) * 2012-08-21 2014-02-27 Uop Llc Inorganic oxides removal and methane conversion process using a supersonic flow reactor
US20140058150A1 (en) * 2012-08-21 2014-02-27 Uop Llc Removal of nitrogen containing compounds and methane conversion process using a supersonic flow reactor
US20140058155A1 (en) * 2012-08-21 2014-02-27 Uop Llc Carbon monoxide removal and methane conversion process using a supersonic flow reactor
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US20150158789A1 (en) * 2013-12-06 2015-06-11 Paul F. Keusenkothen Methods and Systems for Producing Liquid Hydrocarbons

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US5430211A (en) * 1993-10-29 1995-07-04 The Dow Chemical Company Process of preparing ethylbenzene or substituted derivatives thereof
US5856607A (en) * 1996-05-03 1999-01-05 Amoco Corporation Process for production of ethylbenzene frome dilute ethylene streams
US6130260A (en) * 1998-11-25 2000-10-10 The Texas A&M University Systems Method for converting natural gas to liquid hydrocarbons
US6602920B2 (en) 1998-11-25 2003-08-05 The Texas A&M University System Method for converting natural gas to liquid hydrocarbons
US20040002553A1 (en) * 1998-11-25 2004-01-01 The Texas A&M University System Method for converting natural gas to olefins
US7119240B2 (en) 1998-11-25 2006-10-10 The Texas A&M University System Method for converting natural gas to olefins
US6783659B2 (en) * 2001-11-16 2004-08-31 Chevron Phillips Chemical Company, L.P. Process to produce a dilute ethylene stream and a dilute propylene stream
US6790342B1 (en) 2001-11-16 2004-09-14 Chevron Phillips Chemical Company Lp Process to produce a dilute ethylene stream and a dilute propylene stream
US8454911B2 (en) 2005-12-23 2013-06-04 Exxonmobil Chemical Patents Inc. Methane conversion to higher hydrocarbons
US8455707B2 (en) 2005-12-23 2013-06-04 Exxonmobil Chemical Patents Inc. Methane conversion to higher hydrocarbons
US20070191664A1 (en) * 2005-12-23 2007-08-16 Frank Hershkowitz Methane conversion to higher hydrocarbons
US7943808B2 (en) 2005-12-23 2011-05-17 Exxonmobilchemical Patents Inc. Methane conversion to higher hydrocarbons
US8545580B2 (en) 2006-07-18 2013-10-01 Honeywell International Inc. Chemically-modified mixed fuels, methods of production and uses thereof
US8980802B2 (en) 2006-07-18 2015-03-17 Honeywell International Inc. Chemically-modified mixed fuels, methods of production and uses thereof
US20110123405A1 (en) * 2007-06-04 2011-05-26 Keusenkothen Paul F Pyrolysis Reactor Conversion of Hydrocarbon Feedstocks Into Higher Value Hydrocarbons
US8303803B2 (en) 2007-06-04 2012-11-06 Exxonmobil Chemical Patents Inc. Pyrolysis reactor conversion of hydrocarbon feedstocks into higher value hydrocarbons
US7914667B2 (en) 2007-06-04 2011-03-29 Exxonmobil Chemical Patents Inc. Pyrolysis reactor conversion of hydrocarbon feedstocks into higher value hydrocarbons
US20080300438A1 (en) * 2007-06-04 2008-12-04 Keusenkothen Paul F Conversion of co-fed methane and hydrocarbon feedstocks into higher value hydrocarbons
US20090008292A1 (en) * 2007-06-04 2009-01-08 Keusenkothen Paul F Pyrolysis reactor conversion of hydrocarbon feedstocks into higher value hydrocarbons
US8106248B2 (en) 2007-06-04 2012-01-31 Exxonmobil Chemical Patents Inc. Conversion of co-fed methane and hydrocarbon feedstocks into higher value hydrocarbons
US8119076B2 (en) 2007-06-04 2012-02-21 Exxonmobil Chemical Patents Inc. Pyrolysis reactor conversion of hydrocarbon feedstocks into higher value hydrocarbons
US20100126907A1 (en) * 2008-11-24 2010-05-27 Chun Changmin Heat Stable Formed Ceramic, Apparatus And Method Of Using The Same
US8278231B2 (en) 2008-11-24 2012-10-02 Exxonmobil Chemical Patents Inc. Heat stable formed ceramic, apparatus and method of using the same
US20100130803A1 (en) * 2008-11-25 2010-05-27 Keusenkothen Paul F Conversion of Co-Fed Methane and Low Hydrogen Content Hydrocarbon Feedstocks to Acetylene
US8748686B2 (en) 2008-11-25 2014-06-10 Exxonmobil Chemical Patents Inc. Conversion of co-fed methane and low hydrogen content hydrocarbon feedstocks to acetylene
US20100292523A1 (en) * 2009-05-18 2010-11-18 Frank Hershkowitz Pyrolysis Reactor Materials and Methods
US8512663B2 (en) 2009-05-18 2013-08-20 Exxonmobile Chemical Patents Inc. Pyrolysis reactor materials and methods
US20100288617A1 (en) * 2009-05-18 2010-11-18 Frank Hershkowitz Pyrolysis Reactor Materials and Methods
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US20100292522A1 (en) * 2009-05-18 2010-11-18 Chun Changmin Stabilized Ceramic Composition, Apparatus and Methods of Using the Same
US9441166B2 (en) 2009-05-18 2016-09-13 Exxonmobil Chemical Patents Inc. Pyrolysis reactor materials and methods
US8399372B2 (en) 2009-05-18 2013-03-19 Exxonmobil Chemical Patents Inc. Stabilized ceramic composition, apparatus and methods of using the same
US8821806B2 (en) 2009-05-18 2014-09-02 Exxonmobil Chemical Patents Inc. Pyrolysis reactor materials and methods
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US8734729B2 (en) 2009-05-18 2014-05-27 Exxonmobil Chemical Patents Inc. Stabilized ceramic composition, apparatus and methods of using the same
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US20140058152A1 (en) * 2012-08-21 2014-02-27 Uop Llc Inorganic oxides removal and methane conversion process using a supersonic flow reactor
US20140058150A1 (en) * 2012-08-21 2014-02-27 Uop Llc Removal of nitrogen containing compounds and methane conversion process using a supersonic flow reactor
US20140058154A1 (en) * 2012-08-21 2014-02-27 Uop Llc Nitrogen removal and methane conversion process using a supersonic flow reactor
US20140058155A1 (en) * 2012-08-21 2014-02-27 Uop Llc Carbon monoxide removal and methane conversion process using a supersonic flow reactor
US20150158789A1 (en) * 2013-12-06 2015-06-11 Paul F. Keusenkothen Methods and Systems for Producing Liquid Hydrocarbons
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DE69005275D1 (en) 1994-01-27
DE69005275T2 (en) 1994-03-31
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JP2832492B2 (en) 1998-12-09
FR2655038A1 (en) 1991-05-31

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